CN107923126A

CN107923126A - The manufacture method and laminated body of sheet material, sheet material

Info

Publication number: CN107923126A
Application number: CN201680045603.0A
Authority: CN
Inventors: 盘指豪; 酒井红; 野口裕; 野口裕一
Original assignee: Oji Paper Co Ltd
Current assignee: New Oji Paper Co Ltd; Oji Holdings Corp
Priority date: 2015-08-05
Filing date: 2016-08-05
Publication date: 2018-04-17
Also published as: EP3333316A4; US20180230279A1; WO2017022848A1; US10899899B2; KR20180037191A; EP3333316A1; TW201716226A

Abstract

Problem of the present invention is, in the sheet material for having used the microfibre through importing substituent, while keeping high transparency, improves the intensity under the conditions of how wet.The sheet material of the present invention contains metal more than microfibre and divalence with ionic substituent, its mist degree is less than 10.0%.

Description

The manufacture method and laminated body of sheet material, sheet material

Technical field

The present invention relates to the manufacture method and laminated body of sheet material, sheet material.The sheet material of the present invention is wet in addition to transparent height Mechanical properties under profit state are also excellent, the various uses such as packaging material suitable for requiring the transparency.In addition, the present invention's gives The sheet material of mode is determined in addition to transparent height, and the mechanical properties under moisture state are also excellent, and suppress the Huang under hot conditions Become, suitable for various uses such as optical materials.

Background technology

In recent years, because petroleum resources substitute and environmental consciousness is surging, it is conceived to and make use of reproducible natural fiber Material.In natural fiber, the cellulose fibre that 10~50 μm of fibre diameter, the particularly cellulose fibre (paper pulp) from timber Paper products are mainly used for, are widely used so far.

Additionally, it is known that cellulose fibre is the microfibre shape cellulose that fibre diameter is less than 1 μm.Contain microfibre In the sheet material of shape cellulose, because the contact of fiber to each other substantially increases, tensile strength greatly improves.In addition, because Fiber width is shorter than the wavelength of visible ray, so transparency greatly improves.Manufacture method as microfibre, it is known to：For The easy miniaturization of fibrous raw material (fibrillation), fiber original is directed into by substituent with electrostatic and/or three-dimensional functionality Method (such as patent document 1~4) in material.

On the other hand, on the sheet material containing microfibre shape cellulose, from raising barrier properties for gases etc. research Improvement.Such as the manufacture method of the barrier properties for gases laminated body proposed in patent document 5 is that have high barrier to vapor, oxygen Laminated body manufacture method, it includes the 1st application step and the 2nd application step, wherein, the 1st application step is in base material 1st liquid of the fine cellulose fiber that upper carboxyl-content of the coating containing cellulose is 0.1~3mmol/g, the 2nd coating step Suddenly it is that the portion's of being applied coating of above-mentioned 1st liquid in above-mentioned base material contains from layered inorganic compound, crosslinking agent, inorganic gold Belong to more than a kind of the 2nd liquid selected in salt and organic metal salt.In addition, the laminated body proposed in patent document 6 be have it is excellent The laminated body of different water resistance, it is set on base material contains cellulose nano-fibrous and metal salt coating layer, wherein, the fibre The plain nanofiber of dimension is that anion-modified (carboxy methylation or carboxylation) is cellulose nano-fibrous, and metal salt is trivalent metal salt. In addition, even if the barrier properties for gases laminated body proposed in patent document 7 is using cellulose and also has under high humidity conditions The barrier properties for gases laminated body of good gas barrier, is equipped with base material：Containing with the cellulose nano-fibrous of carboxyl Layer (A) and the layer (B) containing polyvalent metal compounds, above-mentioned layer (A) connect with above-mentioned layer (B), upper in above-mentioned layer (A) State the cellulose nano-fibrous polyvalent metal ion progress ionomer for utilizing and being derived from above-mentioned polyvalent metal compounds.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2008-308802 publications

Patent document 2：Japanese Unexamined Patent Publication 2010-254726 publications

Patent document 3：Japanese Unexamined Patent Application Publication 2012-511596 publications

Patent document 4：International Publication WO2013/073652

Patent document 5：Japanese Unexamined Patent Publication 2011-224545 publications

Patent document 6：Japanese Unexamined Patent Publication 2014-193580 publications

Patent document 7：Japanese Unexamined Patent Publication 2014-223737 publications

The content of the invention

Problem to be solved by the invention

Though having used the sheet material of the microfibre through importing substituent has high transparency, because of depositing for hydrophilic And cause hygroscopicity high, swelling/fracture occurs under more wet bar parts, there is the worry for causing strength deterioration.However, patent document 5~7 any patent document is not all for the purpose of sheet properties are improved in terms of water vapor barrier property, water imbibition, but to have in mind In improved under keeping transparent state it is how wet under the conditions of intensity.If the sheet material containing the microfibre through importing substituent Can take into account high transparency with it is how wet under the conditions of it is certain more than intensity, then preferably.

Solution to the problem

On the other hand, the inventors of the present invention to solve the above-mentioned problems, for the substituent in the slurry stage before sheet material The countermeasures such as the substituent disengaging after disengaging, the change of substituent degree of neutralization, sheet material are furtherd investigate.Moreover, at present, as into One step reduces the method to the load of step, has attempted to use metal ion more than divalence as the end-capping reagent of substituent. As a result, under conditions of suitable control, pass through metal ion more than the piece timber-used divalence to the microfibre with substituent Handled, can obtain while high transparency is kept, even if will not occur swelling/fracture in a wetted condition, and had There is the sheet material of certain above intensity, so as to complete the present invention.In addition, the inventors of the present invention find by it is above-mentioned through divalence more than Metal ion treatment sheet material, further handled using the salt of weak acid, sheet material xanthochromia can inhibit, so as to complete this hair It is bright.

The present invention is to provide following manner.

[1] a kind of sheet material (hereinafter also referred to " sheet material of first method "), it contains with the fine of ionic substituent Metal more than fiber and divalence, its mist degree are less than 10.0%.

[2] sheet material as described in [1], wherein, the content of metal more than divalence is more than 0.10mmol/g.

[3] sheet material as described in [1] or [2], wherein, microfibre is that have from the group from phosphoric acid, from carboxylic acid Group and group from sulfuric acid in the microfibre shape fiber of the one or more selected as ionic substituent Element.

[4] sheet material as any one of [1]~[3], its tensile strength in a wetted condition for 10.0MPa with On.

[5] sheet material as any one of [1]~[4], its tensile modulus of elasticity in a wetted condition is 0.7GPa More than.

[6] a kind of sheet material (hereinafter also referred to " sheet material of second method "), it contains with the fine of ionic substituent Metal more than fiber and divalence, wherein, xanthochromia degree change (Δ YI) meets following formula (1)：

Δ YI=YI₂-YI₁≤20···(1)

Wherein, YI₁Represent the yellow chromaticity before vacuum drying, YI when progress 4 is small at 200 DEG C₂Expression carries out 4 at 200 DEG C Yellow chromaticity after hour vacuum drying.

[7] sheet material as described in [6], wherein, the content of metal more than divalence is more than 0.10mmol/g.

[8] sheet material as described in [6] or [7], wherein, microfibre is that have from the group from phosphoric acid, from carboxylic acid Group and group from sulfuric acid in the microfibre shape fiber of the one or more selected as ionic substituent Element.

[9] sheet material as any one of [6]~[8], it contains selects at least from alkali or alkaline earth metal It is a kind of.

[10] sheet material as any one of [6]~[9], wherein, microfibre is that have from the group from phosphoric acid And microfibre shape cellulose of the one or two selected in the group from carboxylic acid as ionic substituent, and sulfur content For below 0.05mmol/g.

[11] sheet material as any one of [6]~[10], its tensile strength in a wetted condition for 20.0MPa with On.

[12] sheet material as any one of [6]~[11], its tensile modulus of elasticity in a wetted condition are More than 0.7GPa.

[13] a kind of laminated body, its sheet material any one of [1]~[12] at least on side formed with inorganic Layer and/or organic layer.

[14] a kind of manufacture method of sheet material, it includes：Sheet material is prepared from the microfibre with ionic substituent Step；And the step of being handled using the salt from strong acid of metal more than divalence prepared sheet material.

[15] manufacture method of the sheet material as described in [14], it includes：The salt pair further formed using weak acid with highly basic The step of processed sheet material is handled.

The effect of invention

The sheet material of the first method obtained by the present invention has high transparency, and mechanical properties in a wetted condition are excellent It is different.The sheet material of the second method obtained by the present invention has high transparency, and mechanical properties in a wetted condition are excellent.This Outside, xanthochromia is suppressed.

Brief description of the drawings

Fig. 1 is the calibration curve of manufactured aluminium import volume in embodiment.

Fig. 2 is the calibration curve of manufactured magnesium import volume in embodiment.

Fig. 3 is the calibration curve of manufactured sulphur in embodiment.

Fig. 4 is the calibration curve of manufactured sodium import volume in embodiment.

Fig. 5 is the calibration curve of manufactured calcium import volume in embodiment.

Embodiment

" part " and " % " represents the ratio (mass parts, quality %) based on quality on the premise of no special instruction.On The value of the fiber qualities such as cellulose is on the premise of no special instruction, based on adiabatic drying quality (solid constituent).In addition, numerical value Scope " X~Y " on the premise of no special instruction, the value comprising both ends." A and/or B " are on the premise of no special instruction Refer at least one of A and B, can be only A, may also be only B, can also A and B both sides.

The present invention provides a kind of sheet material, it contains metal more than microfibre and divalence with ionic substituent. This sheet material can be manufactured by the manufacture method comprised the following steps.

(1) the step of preparing sheet material from the microfibre with ionic substituent；And

(2) step handled using the solution of the salt from strong acid of metal more than divalence prepared sheet material Suddenly.

In addition, the present invention provides a kind of sheet material, it contains more than microfibre and divalence with ionic substituent Metal, and xanthochromia degree is with low uncertainty.This sheet material can be manufactured by the manufacture method comprised the following steps.

(1) the step of preparing sheet material from the microfibre with ionic substituent；

(2) step handled using the solution of the salt from strong acid of metal more than divalence prepared sheet material Suddenly；And

(3) the step of salt further formed using weak acid and highly basic handles processed sheet material.

Hereinafter, the manufacture method of sheet material is illustrated first, then the piece to the sheet material obtained by the manufacture method The structure of (thing) and characteristic illustrate material in itself.

[manufacture method of sheet material]

The microfibre with ionic substituent of step (1) by importing ionic substituent in fibrous raw material, And the fibrous raw material with substituent to obtaining carries out miniaturization (fibrillation) processing and obtains.

＜ fibrous raw materials ＞

It is not particularly limited, can be enumerated for example as fibrous raw material：It is organic fiber, inorfil, synthetic fibers etc., hemizygous Into fiber, regenerated fiber.It can be enumerated for example as organic fiber：Cellulose, carbon fiber, paper pulp, chitin, chitosan etc. are derived from Fiber of natural goods etc., but not limited to this.It can be enumerated for example as inorfil：Glass fibre, rock fiber (rock Fiber), metallic fiber etc., but not limited to this.It can be enumerated for example as synthetic fibers：Nylon, vinylon (vinylon), sub- second Alkene (vinylidene), polyester, polyolefin (such as polyethylene, polypropylene etc.), polyurethane, acryl, polyvinyl chloride, aromatics gather Acid amides etc., but not limited to this.It can be enumerated for example as semisynthetic fibre：Acetate, triacetate, protein fibre (Promix) Deng, but not limited to this.It can be enumerated for example as regenerated fiber：Artificial silk, copper ammonia fiber, high wet modulus viscosity glue artificial silk (polynosic rayon), Lyocell fibers (Lyocell), tencel fiber (Tencel) etc., but not limited to this.

In addition, fibrous raw material used in the present invention is not particularly limited, readily seen from the importing of aftermentioned substituent is made Point sets out, and it is expected containing hydroxyl or amino.

From obtain easily, it is cheap from the viewpoint of, as fibrous raw material, preferably using paper pulp.As paper pulp, selected from timber Paper pulp, non-wood pulp, de inked pulp.It can be enumerated for example as wood pulp：Broad leaf tree kraft pulp (LBKP), coniferous tree ox Mulberry paper slurry (NBKP), sulfite pulp (SP), soda pulp (Soda Pulp, AP), non-bleached kraft pulp (UKP), oxygen bleaching Chemical pulps such as white kraft pulp (OKP) etc..In addition, it can enumerate for example：Semichemical wood pulp (SCP), chemigroundwood pulp (chemi Ground wood pulp, CGP) etc. semichemical wood pulp；The machinery paper such as photogrammetry pulp mill (GP), thermomechanical pulp (TMP, BCTMP) Slurry etc., is not particularly limited.It can be enumerated for example as non-wood pulp：The silk floss system paper such as cotton linter, velveteen (cotton lint) Slurry；The non-timber such as fiber crops, wheat straw, bagasse system paper pulp；By the cellulose of the isolations such as ascidian, sea grass；Chitin, chitosan etc., have no It is particularly limited to.The de inked pulp for example using waste paper as raw material can be enumerated as de inked pulp, is not particularly limited.Present embodiment Paper pulp can be used alone above-mentioned a kind, can also be mixed with two or more.In above-mentioned paper pulp, from the viewpoint for obtaining easiness Set out, preferably the wood pulp of containing cellulose, de inked pulp.In wood pulp, chemical pulp since cellulose ratio is big, so Fine cellulose fiber yield at fiber miniaturization (fibrillation) is high and the decomposition of cellulose in paper pulp is small, can obtain axis It is more particularly preferred than big long fibre fine cellulose fiber etc., but be not particularly limited.Wherein, brown paper is most preferably selected Slurry, sulfite pulp, but be not particularly limited.In addition, it is following, to use cellulose fibre raw material or microfibre shape fiber The present invention and embodiments thereof or embodiment are illustrated in case of element, those skilled in the art should understand that using it The situation of its fibrous raw material can also be applicable in the explanation.

The importing ＞ of the ionic substituents of ＜

Ionic substituent is imported in fibrous raw material.The method for importing substituent in the fibre is not particularly limited, can Enumerate for example：Oxidation processes, the processing carried out using the compound that covalent bond can be formed with the functional group in cellulose etc..It is so-called " oxidation processes " refer to the processing that the hydroxyl in cellulose is converted into aldehyde radical, carboxyl, for example, TEMPO oxidation processes, using each The processing of kind oxidant (sodium chlorite, ozone etc.).

As oxidation processes an example, such as 8,2485-2491,2007 (Saito of Biomacromolecules can be enumerated Deng) described in method, be not particularly limited.

The processing carried out using the compound that covalent bond can be formed with the functional group in cellulose can be by the following method Implement：In the fibrous raw material of drying regime or moisture state, the compound reacted with the fibrous raw material is mixed, so that Above-mentioned substituent is imported in fibrous raw material.In order to promote reaction when importing, the method heated is especially effective.Import substitution Heat treatment temperature during base is not particularly limited, and is preferably not easy to trigger the temperature of the thermal decomposition of the fibrous raw material, hydrolysis etc. Scope.Such as from the viewpoint of the heat decomposition temperature of cellulose, more preferably less than 250 DEG C, from suppression cellulose hydrolysis Viewpoint is set out, and is more preferably heated with 100~170 DEG C.

As the compound reacted with fibrous raw material, as long as microfibre can be obtained and import ionic substituent, Just it is not particularly limited.

In the case where importing anionic substituent, example can be enumerated as the compound reacted with fibrous raw material Such as：Compound with the group from phosphoric acid, the compound with the group from carboxylic acid, have the group for being derived from sulfuric acid Compound, have compound of group from sulfonic acid etc..From ease of handling and with from the viewpoint of the reactivity of fiber, Preferably there is at least one kind of change selected from the group from phosphoric acid, the group from carboxylic acid and the group from sulfuric acid Compound.These compounds more preferably can form ester and/or ether with fiber, but be not particularly limited.

Use have a case that from phosphoric acid group compound as with the aitiogenic compound of fibrous raw material Under, it is not particularly limited, can is to be selected from such as phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acids, polyphosphonic acid or their salt or ester What is gone out is at least one kind of.In these, it is micro- so as to further improve that phosphate easily and in fibrous raw material is imported from low cost, processing From the viewpoint of refining (fibrillation) efficiency, the more preferably compound with phosphate, but be not particularly limited.

It is not particularly limited, can be enumerated for example as the compound with phosphate：Phosphoric acid, as phosphoric acid lithium salts phosphorus Acid dihydride lithium, two lithium of phosphoric acid hydrogen, tricresyl phosphate lithium, pyrophosphoric acid lithium, polyphosphoric acid lithium.It can also enumerate for example：Sodium salt as phosphoric acid Sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, sodium pyrophosphate, polyphosphate sodium.It can also enumerate for example：As phosphoric acid Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, the PA 800K of sylvite.It can also enumerate for example：As phosphorus The ammonium dihydrogen phosphate of ammonium salt of acid, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate etc..

In these, from phosphate import it is efficient, industrial be easily applicable in from the viewpoint of, be preferably phosphoric acid, phosphoric acid Sodium salt, sylvite, the ammonium salt of phosphoric acid of phosphoric acid, more preferably sodium dihydrogen phosphate, disodium hydrogen phosphate, but be not particularly limited.

In addition, from the viewpoint of the importing of reaction uniformity and group from phosphoric acid is efficient, compound preferably with Aqueous solution form uses, but is not particularly limited.The aqueous solution pH of compound is not particularly limited, the efficiency imported from phosphate It is preferably less than 7 from the viewpoint of height.From the viewpoint of fiber hydrolysis is suppressed, particularly preferably pH3~7, but have no especially Limit.

The compound with the group from carboxylic acid is being used as the compound reacted with fibrous raw material Under, be not particularly limited, can be from the compound with carboxyl, the acid anhydrides and their derivative of the compound with carboxyl In select it is at least one kind of.

It is not particularly limited, can be enumerated for example as the compound with carboxyl：Maleic acid, butanedioic acid, phthalic acid, The dicarboxylic acid compounds such as fumaric acid, glutaric acid, adipic acid, itaconic acid；The tricarboxylic acid compound such as citric acid, aconitic acid.

Acid anhydrides as the compound with carboxyl is not particularly limited, and can be enumerated for example：Maleic anhydride, succinic anhydride, The acid anhydrides of the dicarboxylic acid compounds such as phthalic anhydride, glutaric anhydride, adipic anhydride, itaconic anhydride.

Derivative as the compound with carboxyl is not particularly limited, and can be enumerated for example：With carboxyl compound The acid imide compound of acid anhydrides, have carboxyl compound acid anhydrides derivative.The imidizate of acid anhydrides with carboxyl compound Thing is not particularly limited, and can be enumerated for example：The dicarboxylic acid compounds such as maleimide, succinimide, phthalimide Acid imide compound.

Derivative as the acid anhydrides with carboxyl compound is not particularly limited.It can enumerate for example：Dimethyl maleic acid Acid anhydride, diethyl maleic acid acid anhydride, diphenyl maleic anhydride etc., at least a portion hydrogen atom of acid anhydrides with carboxyl compound are taken The compound of Dai Ji (such as alkyl, phenyl etc.) substitutions.

In the above-mentioned compound with the group from carboxylic acid, go out from the industrial viewpoint for being easily applicable in and easily gasifying Hair, preferably maleic anhydride, succinic anhydride, phthalic anhydride, but be not particularly limited.

The compound with the group from sulfuric acid is being used as the compound reacted with fibrous raw material Under, be not particularly limited, can be selected from sulfuric anhydride, sulfuric acid and their salt and ester it is at least one kind of.In these, from low Cost and sulfate is imported in fibrous raw material so as to from the viewpoint of can further improve miniaturization (fibrillation) efficiency, it is more excellent Sulfuric acid is selected, but is not particularly limited.

By importing substituent in fibrous raw material, so as to improve the fiber dispersion in solution, miniaturization can be improved and (opened It is fine) efficiency.

For the import volume of ionic substituent, as long as abundant miniaturization can carried out, just it is not particularly limited, as after It is described, it is contemplated that to be determined again after the content of the metal more than divalence during as sheet material, substituent import volume.When sheet material of the present invention During containing microfibre with anionic substituent, the import volume (using titration) of preferred substituents is per 1g (quality) The α of the α of 0.005 α of fiber~0.11, more preferably 0.01 α~0.08.Import volume if instead of base is 0.005 more than α, then fiber Easily, the import volume if instead of base is 0.11 below α, then can inhibit the dissolving of fiber for the miniaturization (fibrillation) of raw material.Wherein, α is amount (unit of the functional group, such as hydroxyl, amino that can be reacted with compound contained by every 1g fibrous materials： Mmol/g), above-claimed cpd can produce reaction with fibrous material.

In addition, the measure of the substituent import volume (titration) of fiber surface, can pass through on the premise of no special instruction Following methods are implemented：

Divide the slurry containing microfibre taken containing 0.04g or so solid constituents in terms of adiabatic drying quality, use ion exchange Water is diluted to 50g or so.While the solution is stirred, while conductivity value during measure dropwise addition 0.01N sodium hydrate aqueous solutions Change, the dripping quantity of 0.01N sodium hydrate aqueous solutions when which is become minimum are set to the dripping quantity of titration end-point.Fiber The substitution base unit weight X on plain surface is represented by X (mmol/g)=0.01 (mol/l) × V (ml)/W (g).Wherein, V is：0.01N hydrogen-oxygens Change the dripping quantity (ml) of sodium water solution；W is：Solid constituent (g) contained by slurry containing fine cellulose fiber.

Selected in being from the group from phosphoric acid, the group from carboxylic acid and from the group of sulfuric acid when the substituent of importing It is at least one kind of when, substituent import volume is not particularly limited, and can be set to 0.001~5.0mmol/g.It can also be set to 0.05~ 4.0mmol/g, can also be set to 0.1~2.0mmol/g.

＜ alkali process ＞

As needed, can also be after ionic substituent be imported and in the advance of miniaturization processing described below Row alkali process.By alkali process, cation is supplied to the anionic substituent being directed into fiber, can easily form salt. In addition, from the viewpoint of fiber yield is improved, alkali process is preferably carried out.

The method of alkali process is not particularly limited.Such as can be by being impregnated in aqueous slkali through importing ionic substituent Cellulose fibre and implement.

Contained alkali cpd can be inorganic alkali compound, can also be organo-alkali compound in aqueous slkali.Inorganic base The example of compound is：Hydroxide, carbonate and the phosphate of alkali or alkaline earth metal.More specifically example is：Hydrogen-oxygen Change lithium, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, lithium bicarbonate, potassium carbonate, saleratus, sodium carbonate, bicarbonate Sodium, calcium carbonate, lithium phosphate, potassium phosphate, tertiary sodium phosphate, disodium hydrogen phosphate, calcium phosphate, calcium monohydrogen phosphate.The reality of organo-alkali compound Example be：Ammonia, aliphatic amine, aromatic amine, aliphatic ammonium, aromatic series ammonium, hetero ring type compound and their hydroxide, carbon Hydrochlorate or phosphate.More specifically example is：Ammonia, hydrazine, methylamine, ethamine, diethylamine, triethylamine, propylamine, di-n-propylamine, fourth Amine, diaminoethanes, diaminopropanes, diaminobutane, 1,5-DAP, diamino hexane, cyclohexylamine, aniline, hydroxide Tetramethylammonium, tetraethylammonium hydroxide, hydroxide tetrapropylammonium, tetrabutylammonium hydroxide, hydroxide benzyl trimethylammonium, pyridine, N, N- diformazans Base -4-aminopyridine, ammonium carbonate, ammonium hydrogen carbonate, diammonium hydrogen phosphate (diammomium hydrogen phosphate).

The solvent of aqueous slkali is not particularly limited, and water and/or organic solvent can be used.Preferably there is polarity (water, alcohol etc. Polar organic solvent) solvent, the more preferably water solvent containing water.The particularly preferred example of aqueous slkali is sodium hydroxide Aqueous solution or potassium hydroxide aqueous solution.

PH of the aqueous slkali of cellulose of the dipping through the ionic substituent of importing at 25 DEG C can suitably be set, and be preferably 9 More than, more preferably more than 10, more preferably more than 11.The reason for this is that the yield of cellulose fibre further improves.Appoint In the case of one, pH of the aqueous slkali at 25 DEG C is preferably less than 14.The reason for this is that if pH were more than 14, the processing of aqueous slkali Property reduce.

, can also be before alkali treatment, by the fibre through importing ionic substituent in order to reduce the usage amount of aqueous slkali Cellulose fiber is cleaned.Water and/or organic solvent can be used when clean.In addition, in order to improve treatability, can also be in alkali process Afterwards and following miniaturization before processings, using water and/or organic solvent to alkali-treated through importing ionic substituent Cellulose fibre is cleaned.

＜ miniaturizations (fibrillation) handle ＞

When miniaturization is handled, cellulose fibre is scattered in solvent.As long as the species of solvent can suitably carry out miniaturization ( Referred to as " fibrillation ") processing, just it is not particularly limited, water solvent (mixture of water or water and organic solvent) can be used.As having Solvent can be enumerated for example：The alcohols such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol.Furthermore it is also possible to enumerate Such as：The ketones such as acetone, methyl ethyl ketone (MEK)；The ethers such as diethyl ether, tetrahydrofuran (THF)；Dimethyl sulfoxide (DMSO), dimethyl Formamide (DMF), dimethylacetylamide (DMAc) etc..Organic solvent can be used only a kind, can also use two or more.

Dispersion concentration is preferably 0.1~20 mass %, more preferably 0.5~10 mass %.The reason for this is that if content is More than above-mentioned lower limit, then treatment effeciency can be improved, below above-mentioned upper limit value, then can prevented in fibrillation processing unit Block.

It is not particularly limited as fibrillation processing unit.It can enumerate for example：(stone mortar type crushes for high speed fibre separating machine, grinder Machine), high pressure homogenizer, superhigh-voltage homogenizing machine, Ke Liya mixers (Clearmix), high-pressure impingement type pulverizer, ball mill, pearl Grinding machine, disc type conche, conical refiner (conical refiner).Alternatively, it is also possible to suitably use twin shaft muller, Oscillating mill, the homogeneous mixer under rotation, ultrasonic dispersing machine, beater etc. carry out device of case of wet attrition etc. at a high speed.

The average fiber width of the microfibre shape cellulose fibre handled using miniaturization is not particularly limited, example 1~1000nm can be such as set to, is preferably 2~1000nm, more preferably 2~500nm, more preferably 3~100nm.If The average fiber width of microfibre is more than 1nm, then can inhibit dissolving of the molecule to water, therefore can fully show as micro- The physical property (intensity, rigidity, dimensional stability) of fine fibre.On the other hand, if average fiber width is below 1000nm, hold Speciality (high transparency, high elastic modulus, low linear expansion coefficient, flexibility) when easily playing as microfibre.In addition, what is obtained is micro- Fine-fibrous cellulose dispersion liquid can also exceed the cellulose fibre of 1000nm containing fiber width, but preferably not contain fiber Width exceedes the cellulose fibre of 1000nm.

In the purposes of high transparency is required to microfibre, if average fiber width is below 30nm, approaching can See the 1/10 of optical wavelength, be not susceptible to visible anaclasis and scattering when laminated body is made in interface, high transparency can be obtained by having Tendency.So average fiber width is not particularly limited, and it is preferably 2nm~30nm, more preferably 2~20nm.From as above institute The laminated body that the microfibre stated obtains is because usually become fine and close structure, and intensity is high, visible light scattering is few, therefore Also high transparency can be obtained.

Average fiber width is determined as follows implementation.The slurry containing microfibre that concentration is 0.05~0.1 mass % is prepared, The slurry is poured and is cast from the carbon film coated grid of hydrophilized processing, tem observation sample is made.Containing the wide fiber of width In the case of, the SEM that can also observe the surface cast on glass schemes.According to the width of the fiber of composition, with 1000 times, Any multiplying powers such as 5000 times, 10000 times, 20000 times or 50000 times are observed with electron microscope image.Wherein, will try Sample, observation condition, multiplying power are adjusted to meet following conditions.

(1) any place in observation image draws a straight line X, and the fiber and straight line X for having more than 20 intersect.

(2) the straight line Y vertically intersected with the straight line is marked in identical image, the fiber and the straight line for there are more than 20 Y intersects.

Observation image to meeting above-mentioned condition, visually reads the width with straight line X, straight line the Y fiber to interlock.So The image of more than 3 groups underlapped surface portion is at least observed, for each image reading and straight line X, straight line the Y fiber to interlock Width.So read the width of at least 20 × 2 × 3=120 root fibers.The width of average fiber is the fiber so read The average value of width.

Fibre length is not particularly limited, more preferably more than 0.1 μm.If fibre length is more than 0.1 μm, work as manufacture It is preferable from the viewpoint of sheet material tearing strength is abundant during aftermentioned sheet material.Fibre length can utilize TEM, SEM, AFM Image analysis and obtain.Above-mentioned fibre length is the fibre length accounted for more than 30 mass % of microfibre.

The axis ratio (fibre length/fiber width) of fiber is not particularly limited, and is preferably 20~10000 scopes.If axis Than for more than 20, then from it is easy form sheet material containing microfibre from the viewpoint of, be preferable.If axis ratio is less than 10000, It is preferable then from the viewpoint of slurry viscosity reduction.

Handled using miniaturization, can obtain the dispersion liquid (slurry) of above-mentioned microfibre shape cellulose.Fine fibre herein The concentration of fibrous cellulose is, for example, 0.1~20 mass %, or 0.5~10 mass %.

＜ sheet materials ＞

From the dispersion liquid (slurry) of the microfibre shape cellulose fibre handled using miniaturization, sheet material is prepared.Piece The preparation method of material is not particularly limited, typically, can be according to following copy paper methods, rubbing method etc..

(copy paper method)

The continuous paper machine such as fourdrinier wire formula, cylinder, inclined wire formula used in usual copy paper can be utilized, or by these groups Conjunction multilayer collocation paper machine and write by hand etc. known in copy paper method to slurry containing microfibre carry out copy paper, and by with it is general The same method of logical paper carries out sheet material.I.e., it is possible to be filtered, be dehydrated to slurry containing microfibre on reticulate pattern, and obtain To after l Water Paper state sheet material, by being pressurizeed, dry, so as to obtain sheet material.The concentration of slurry is not particularly limited, and is preferably 0.05~5 mass %, takes considerable time if concentration is too low in filtering, if instead excessive concentration can not obtain Even sheet material, thus it is not preferred.When being filtered, be dehydrated to slurry, as filter cloth when filtering, it is not particularly limited, it is important Be that microfibre will not be by, and the rate of filtration will not be excessively slow.As this filter cloth, it is not particularly limited, preferably by having Sheet material, fabric, the perforated membrane of machine polymer composition.It is not particularly limited as organic polymer, is preferably poly terephthalic acid The non-cellulose class organic polymers such as second diester, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) (PTFE).Specific enumerable such as hole 0.1~20 μm of footpath, the perforated membrane of such as 1 μm of polytetrafluoroethylene (PTFE), 0.1~20 μm of aperture, such as 1 μm of poly terephthalic acid second The fabric etc. of diester, polyethylene, is not particularly limited.

(rubbing method)

Rubbing method is to be coated on by that will contain microfibre slurry on base material, and dries it and formed containing microfibre Layer, which is peeled off from base material, so as to obtain the method for sheet material., can be continuously by using apparatus for coating and strip substrate Produce sheet material.The material of base material is not particularly limited, and the high sheet material of the wettability to the slurry containing microfibre can press down in drying Film-making material contraction etc., preferably selects the sheet material that the sheet material formed after drying can be easily peeled off.Wherein, it is preferably resin Plate or metallic plate, but be not particularly limited.Used wherein it is possible to which suitable sheet material or lamination is used alone.It can be used for example： The resin plates such as acrylic plate, polyethylene terephthalate plate, vinyl chloride sheet, polystyrene board, polyvinylidene chloride plate；Aluminium The metallic plates such as plate, photo zincography, copperplate, iron plate；And sheet material obtained from having carried out oxidation processes to their surface and stainless Steel plate, brass sheet etc., are not particularly limited.When that will contain microfibre slurry and be coated on base material, as long as using can be above-mentioned The various coating machines of given amount of slurry are coated with base material.It is not particularly limited, can be used for example：Roll coater, intaglio plate coating Machine, die coater, curtain application device, Bracewell coater, knife type coater, bar coater, Kohler coater etc., wherein utilizing Such as the method for the coating method such as the coating of die coating, curtain type, spraying coating, airblade coating is effective in terms of even spread. In addition, as be described hereinafter, when sheet material is made laminated body etc., there is also situation about can not be peeled off from base material.

(amount of slurry)

The thickness of prepared sheet material is not particularly limited, and can suitably be set according to purposes, can be according to the completion list of sheet material Position area weight or thickness, copy paper or coating etc. are carried out after measuring amount of slurry.

(dehydration, drying)

After copy paper or coating etc., it is dehydrated and/or is dried as needed, carries out sheet material.Further, since step afterwards Handled in rapid using the solution of the salt from strong acid of metal more than divalence, so dehydration, drying can be carried out to water Untill point being removed to certain degree, can not exclusively it carry out to as obtaining as the situation of the sheet material of common final thing. It is not particularly limited as dewatering, dewatering usually used when for example manufacturing paper can be enumerated, preferably utilize fourdrinier wire, circle After net, inclined wire etc. are dehydrated, the method that is dehydrated of roll-in is recycled.In addition, be not particularly limited as drying means, can Used method when for example manufacturing paper is enumerated, preferably for example：Roller drier, Yankee drying cylinder (yankeedryer), hot air drying The methods of dry, infrared heater.

It is not particularly limited as drying means, can is non-contact drying method, or while constraint sheet material one The either method of the method for side drying, or combinations thereof.

It is not particularly limited, can be used for example as non-contact drying method：By hot wind, infrared ray, far infrared or Near infrared ray is heated and dry method (heat drying method), the method (boulton process) for being set to vacuum and drying. Can be the combination of heat drying method and boulton process, but generally use heat drying method.Using infrared ray, far infrared or Infrared equipment, far infrared apparatus or near infrared gear can be used to implement for the drying that near infrared ray carries out, and be not particularly limited.Heating Heating-up temperature during seasoning is not particularly limited, and is preferably set to 40~120 DEG C, is more preferably set to 40~105 DEG C.If Heating-up temperature is more than above-mentioned lower limit, can make decentralized medium volatilize rapidly, below above-mentioned upper limit value, then can inhibit and add The required cost of heat and the discoloration caused by heat for suppressing microfibre.

(other fibers)

When preparing sheet material, though it is not particularly limited, can also be by above-mentioned microfibre, above-mentioned micro- with least one or more Fiber (hereinafter referred to as " accessory fibers ") beyond fine fibre is mixed and prepared.It can be enumerated for example as accessory fibers：It is inorganic Fiber, organic fiber, synthetic fibers etc., semisynthetic fibre, regenerated fiber, are not particularly limited.It can be enumerated as inorfil Such as：Glass fibre, rock fiber, metallic fiber etc., but not limited to this.It can be enumerated for example as organic fiber：Cellulose, carbon Fiber, paper pulp, chitin, chitosan etc. are derived from fiber of natural goods etc., but not limited to this.Example can be enumerated as synthetic fibers Such as：Nylon, vinylon, sub- ethene, polyester, polyolefin (such as polyethylene, polypropylene etc.), polyurethane, acryl, polychlorostyrene second Alkene, aromatic polyamides etc., but not limited to this.It can be enumerated for example as semisynthetic fibre：Acetate, triacetate, protein are fine Dimension etc., but not limited to this.It can be enumerated for example as regenerated fiber：Artificial silk, copper ammonia fiber, high wet modulus viscosity glue artificial silk, Lay Sai Er fibers, tencel fiber etc., but not limited to this.As needed, chemically processing, fibrillation processing can be carried out to accessory fibers Deng processing.

Mixing is not particularly limited, such as before copy paper or coating, can be by adding it in slurry containing microfibre Its fiber and implement.When carrying out chemically processing, fibrillation processing to accessory fibers when processing, then it is being mixed with microfibre Afterwards, can also chemically be handled, fibrillation processing etc. processing, can also to accessory fibers carry out chemically processing, fibrillation Mixed again with microfibre after the processing such as processing.From easily mixed uniformly viewpoint, preferably with equal extent The fiber of avarage fiber diameter is mixed with each other.

In the case where mixing accessory fibers, the accessory fibers additive amount in the total amount of microfibre and accessory fibers has no It is particularly limited to, is preferably below 50 mass %, more preferably below 40 mass %, more preferably below 30 mass %.It is special You Xuanwei not below 20 mass %.

In addition, when preparing sheet material, hydrophilic macromolecule can also be added.It can be enumerated for example as hydrophilic macromolecule：It is poly- Ethylene glycol, cellulose derivative (hydroxyethyl cellulose, carboxyethyl cellulose, carboxymethyl cellulose etc.), casein, dextrin, shallow lake Powder, modified starch, polyvinyl alcohol, modified polyvinylalcohol (acetoacetylated polyvinyl alcohol etc.), polyethylene oxide, polyethylene pyrrole Pyridine ketone, polyvinyl methyl ether, polyacrylate, polyacrylamide, alkyl acrylate copolymer, urethane esters are coughed up to be total to Polymers etc., is not particularly limited.

Alternatively, it is also possible to replace substitution hydrophilic macromolecule using hydrophily low molecular compound.It is low as hydrophily Molecular compound can be enumerated for example：Glycerine, erythrite, xylitol, D-sorbite, galactitol (galactitol), mannose Alcohol, ethylene glycol, diethylene glycol, propane diols, dipropylene glycol, butanediol etc., are not particularly limited.

The mixing of hydrophilic macromolecule or hydrophily low molecular compound is not particularly limited, for example, can in copy paper or Before coating, implemented by adding hydrophilic macromolecule or hydrophily low molecular compound in slurry containing microfibre.Relatively It is excellent in 100 mass parts of microfibre solid constituent, additive amount when adding hydrophilic macromolecule or hydrophily low molecular compound Elect 1 to 200 mass parts as, more preferably 1 to 150 mass parts, more preferably 2 to 120 mass parts, particularly preferably 3 to 100 mass parts, are not particularly limited.

＜ uses the processing ＞ of metal more than divalence

In the present invention, in step (2), the microfibre with ionic substituent utilizes the source of metal more than divalence Handled from the solution of the salt of strong acid.On the premise of no special instruction, metal can be ion, element (atom) or chemical combination Any state of thing.In addition, when sheet material contains certain metal, which can be with such as ion, element (atom) in sheet material Or the form of compound exists, and can be analyzed by x-ray fluorescence analysis.Metal more than divalence is preferably divalent metal Or trivalent metal.The example of divalent metal atom can be enumerated for example：Magnesium (Mg), calcium (Ca), nickel (II) (Ni (II)), cobalt (II) (Co (II)), copper (II) (Cu (II)), manganese (Mn), iron (II) (Fe (II)), lithium (Li), vanadium (II) (V (II)), zirconium (Zr) and zinc (Zn).The example of trivalent metal can be enumerated for example：Aluminium (Al) and iron (III) (Fe (III)).From the intensity improved under moisture state Set out etc. viewpoint, in these, more preferably aluminium, magnesium, calcium, copper, iron and zinc, particularly preferably aluminium, magnesium and zinc.Metal can be used only It is a kind of, can also use it is two or more.

Metal more than divalence is used for the processing of sheet material in the form of the solution of water-soluble salt from strong acid.It is derived from The salt of strong acid refers to the salt of the strong acid from sulfuric acid, hydrochloric acid or nitric acid.Faintly acid~highly acid is presented in the aqueous solution of salt.It is preferred that make With the high salt of the solubility to water, the concrete example as this metal salt can be enumerated for example：Aluminum sulfate, magnesium sulfate, alum, Alum, sulfuric acid ferric trichloride, are preferably aluminum sulfate and magnesium sulfate.

The method of processing is not particularly limited.Such as it can implement by the following method：By what is obtained by above-mentioned steps Sheet material is impregnated in the salt from strong acid of metal more than divalence is dissolved in appropriate solvent obtained from a few minutes in solution ~a few houres.As solvent, as long as the salt from strong acid of the metal used in dissolving more than divalence, just without especially limit It is fixed, preferably using water or aqueous water solvent.Impregnating ratio can suitably be set, such as relative to 1 mass parts of sheet material, can be used 1 ~100 mass parts, the solution preferably using 1.5~50 mass parts.

The amount of used metal salt is preferably that can form ion with most of ionic substituent being directed into sheet material To amount.Such as can be used import substituent possessed by ionic substituent at least more than 50%, be preferably more than 60%, More preferably more than 70%, it is more preferably more than 80%, more preferably more than 90% amount that can form ion pair.Or Person, in the case where ionic substituent is phosphate, relative to phosphate 1mmol, if the salt of trivalent metal, then uses 0.3~3.0mmol, is preferably 0.2~2.0mmol, more preferably 0.5~1.5mmol.Using other groups or other salt In the case of, those skilled in the art are contemplated that valence mumber, and the above-mentioned amount based on phosphate and trivalent metal salt, suitably determines substantial amount Chemical equivalent.

The solution concentration of the salt from strong acid of metal more than divalence also depends on dissolubility of the used salt to water, More than 0.05% can be set to, is preferably more than 0.1%, more preferably more than 0.15%.Upper limit value can also determine from economic point of view It is fixed, but be preferably less than 15% from the viewpoint of the sheet material transparency is ensured, more preferably less than 10%.

After being handled using metal salt, carry out cleaning as needed and/or be dehydrated/dry, can obtain as final thing Sheet material.Clean using water or water solvent, be preferably that water is implemented.Dehydration/drying can be by the above sheetization in this The method of explanation is implemented.

It is believed that handled by using the solution of the salt from strong acid of metal more than divalence, the divalence of generation with On metal ion and sheet material on substituent ionic base formed ion pair, formed insoluble or slightly solubility (non-hydrophilic) Cross-linked structure.Thus it is believed that the water resistance increase of sheet material, intensity in a wetted condition improve.In addition, in the present invention, warp After sheet material, handled using the solution of the salt from strong acid, by handling sheet material, can obtain high transparency.Root According to the research of the inventors of the present invention, it is known that in the slurry form stage before sheet material, handled with the solution of the salt from strong acid, Then in the case of carrying out sheet material, in sheet material, the transparency reduces.

＜ uses the processing ＞ of salt of weak acid

In step (3), the sheet material that the solution of the salt further formed using weak acid and highly basic obtains step (2) carries out Processing.In the present invention, step (3) can be carried out, step (3) can not also be carried out.

So-called " weak acid " refers to acid of the acid ionization constant (pKa) than strong acid bigger used in step (2), which forms The salt from strong acid of metal more than divalence, is, for example, formic acid, acetic acid, carbonic acid.Highly basic refers to that dissociation constant of a base pKb is pKb ＜ 0 (for Kb when, Kb ＞ 1) alkali, be typically：The hydroxide of alkali metal, tetra-allkylammonium or alkaline-earth metal etc..More specifically may be used Enumerate for example：Lithium, sodium, potassium, rubidium, caesium, tetramethylammonium, calcium, strontium, barium, europium, the hydroxide of thallium or guanidine.Preference is sodium, potassium or calcium Hydroxide.

Weak acid is used for sheet material with the salt that highly basic is formed in the form of the solution of the salt formed with that can be dissolved in the highly basic of water Processing.The salt formed as weak acid and highly basic, preferably using the high metal salt of the solubility to water, the tool as this metal salt Body example has：Sodium acetate, sodium citrate, sodium lactate, natrium malicum, sodium tartrate, calcium acetate, sodium acid carbonate, potassium acetate, bicarbonate Potassium, sodium carbonate, potassium carbonate, disodium hydrogen phosphate.The salt that weak acid and highly basic are formed can be used only it is a kind of, can also use two kinds with On.

Processing method is not particularly limited.Such as it can implement by the following method：The piece that will be obtained by above-mentioned steps (2) Material is impregnated in the salt that weak acid and highly basic are formed is dissolved in appropriate solvent obtained from a few minutes~a few houres in solution.As Solvent, as long as salt used in dissolving, is just not particularly limited, preferably using water or aqueous water solvent.Impregnating ratio can fit Work as setting, such as relative to 1 mass parts of sheet material, 1~100 mass parts, the solution preferably using 1.5~50 mass parts can be used.

It is preferred that the amount of used salt is that can will be considered to be directed into the anion of salt in sheet material, from step (2) (such as hydrogen sulfate ion HSO₄ ^-) from the amount of sheet material dissociation, the salt of the step (2) is metal more than divalence from strong acid Salt.Such as in the case where ionic substituent is phosphate, relative to phosphate 1mmol, if producing 1 valency Weak Acid Ion (such as acetic acid ion CH₃COO^-Or carbonic acid hydrogen ion HCO₃ ^-) salt, then using 0.1~1.0mmol, preferably using 0.13~ 1.3mmol, more preferably using 0.16~0.5mmol.In the case of using other salt, institute can be contemplated in those skilled in the art The valence mumber of Weak Acid Ion is produced, above-mentioned amount during based on 1 valency Weak Acid Ion of generation is appropriate to determine substantial amount as chemical equivalent.

The solution concentration of salt also depends on dissolubility of the used salt to water, can be set to more than 0.1%, be preferably More than 0.5%, more preferably more than 1.0%.Upper limit value can be determined according to economic viewpoint, be preferably less than 35%, more preferably For less than 30%.

After being handled using metal salt, carry out cleaning as needed and/or be dehydrated/dry, can obtain as final thing Sheet material.Clean and implemented using water or water solvent (being preferably water).Dehydration/drying can be said in this by the above sheetization Bright method is implemented.

By using the processing in (3) the step of weak acid and the salting liquid of highly basic formation, can make to think to be directed into sheet material In, the anion of salt from step (2) (such as HSO₄ ^-) dissociation, the salt of the step (2) is the source of metal more than divalence From the salt of strong acid.Thus, it is believed that it can inhibit the fiber oxidation caused by the anion from strong acid and decompose, obtained sheet material xanthochromia Suppressed.

The sodium salt of phosphoric acid is used to import phosphate as ionic substituent in the OH bases of cellulosic material in addition, working as When, state cellulose-the O-P (=O) (- O after importing^-Na⁺)(-O^-Na⁺) represent.To metal more than the piece timber-used divalence The salt from strong acid handled after, the hydrophilic group (- O at uncrosslinked position there are H-type substituent^-H⁺).In this case, The distinctive anti-flammability mechanism of phosphate is shown under high temperature and humidity, promotes charcoal to form (char formation), therefore easy brown Change.It is therefore contemplated that further using the salt that weak acid and highly basic are formed to the salt from strong acid using metal more than divalence into Gone processing sheet material handled, can make with the hydrophilic group of ionic substituent existing for H-type be formed as salt form (such as- O^-Na⁺), so that it is reduced, the charcoal that can inhibit under high temperature is formed.Pass through these effects, it is believed that obtained sheet yellowness can be suppressed Become.

[structure, the characteristic of sheet material]

To the sheet material of sheet material that is obtained by above-mentioned manufacture method, (thing) structure and characteristic describe in itself below.

＜ total light transmittances ＞

The total light transmittance of sheet material refers to the value measured according to JIS standard Ks 7361 using haze meter.

Total light transmittance by sheet material provided by the invention is preferably more than 80%, and more preferably more than 85%, further Preferably more than 90%.

＜ haze values ＞

The haze value of sheet material refers to the value measured according to JIS standard Ks 7136 using haze meter.Pass through provided by the invention The haze value of the sheet material of one mode is less than 10.0%, is preferably less than 8.0%, more preferably less than 6.0%.Pass through the present invention The haze value of the sheet material of the second method of offer is more preferably less than 10.0%, and more preferably less than 8.0%, more preferably Less than 6.0%.

Think by the way that in obtained sheet material of the invention, low haze valus can be realized in such a way caused by following key elements.Utilize The solution of the salt from strong acid of metal more than divalence is handled, and is located under non-slurry form, after sheet material (in the slurry form stage before sheet material, when being handled using the solution of the salt from strong acid, can prevent the piece observed to reason The transparency reduction of material).In addition, the substituent species for suitably selecting to be directed into fiber, the substituent selected according to situation are led Enter amount, metal (or used metal salt during processing) species, the substitution base unit weight selected according to situation.

＜ yellow chromaticities change ＞

The xanthochromia degree change (Δ YI) of sheet material is expressed from the next：

Δ YI=YI₂-YI₁

Wherein, YI₁Represent the yellow chromaticity before vacuum drying, YI when progress 4 is small at 200 DEG C₂Expression carries out 4 at 200 DEG C Yellow chromaticity after hour vacuum drying.Yellow chromaticity refers to the value measured according to JIS standard Ks 7373.

Following formula (1) is met by the xanthochromia degree change (Δ YI) of the sheet material of second method provided by the invention：

Δ YI=YI₂-YI₁≤20···(1)

Xanthochromia degree change (Δ YI) is preferably less than 15.Think by obtained sheet material of the invention, can so press down Manufacture-yellow colourity changes caused by following key elements.Processing in the step of solution of the salt formed by using weak acid and highly basic (3), Anion (such as the HSO that can make to think to be directed into salt in sheet material, from step (2)₄ ^-) dissociation, it can inhibit the oxygen of fiber Change and decompose, the salt of the step (2) is the salt from strong acid of metal more than divalence.In the sheet material situation through importing phosphate Under, using the salt from strong acid of metal more than divalence to being handled using the salt from strong acid of metal more than divalence The hydrophilic group (- O of existing H-type substituent afterwards^-H⁺) handled, become salt form (such as-O^-Na⁺), so that it subtracts Few, the charcoal thus suppressed under high temperature is formed.In addition, further using the salt that weak acid and highly basic are formed to utilizing gold more than divalence When the sheet material that is handled of the salt from strong acid belonged to is handled, suitably select the concentration of the salt, according to circumstances select Species.

The import volume ＞ of metal more than ＜ divalence

Metal import volume (mmol/g) more than the divalence in sheet material can use the following institute of such as fluorescent x-ary analysis Measure with stating.

First, the method for making as calibration curve, prepares (such as make similar with the composition and form of measure object sheet material With filter paper) and analytical element content (mmol) known to sample, the X-ray that the sample is measured using x-ray fluorescence analysis is strong Degree.Herein, metal more than divalence becomes analytical element.Then, based on thus obtained X-ray intensity and analytical element Know content, calibration curve is made.Then, using x-ray fluorescence analysis, the X-ray intensity of measure object sheet material is carried out.Connect , based on thus obtained X-ray intensity and above-mentioned calibration curve, obtain the analytical element content in measure object sheet material (mmol).Then, with the analytical element content divided by the quality (g) of measure object sheet material in obtained measure object sheet material, meter Calculate the import volume (mmol/g) of the metal more than divalence imported in measure object sheet material.Herein, the matter of measure object sheet material Z is measured by Z (g)=W (cm²)×X(g/cm³) × Y (cm) represents (W：Area (the cm of sheet material used in x-ray fluorescence analysis²), X：Sheet density (g/cm³), Y：Sheet thickness (cm)).

Import volume by the metal more than divalence of sheet material provided by the invention is to effectively improve sheet material in wet condition Under intensity amount.Effective dose can be set to more than such as 0.10mmol/g (every sheet material), be preferably 0.25mmol/g (every piece Material) more than.In addition, in the case where ionic substituent possessed by microfibre is from the group of phosphoric acid, it is more than divalence Metal import volume be more preferably more than such as 0.50mmol/g (every sheet material), particularly preferably 0.80mmol/g (every Sheet material) more than.In addition, when importing the group from phosphoric acid in microfibre, aluminium is being imported as metal more than divalence In the case of, its import volume is particularly preferably more than such as 1.0mmol/g (every sheet material).The reason for this is that if set to this number Value, even if then in a wetted condition, sheet material will not be swollen/be broken, it is possible to find tensile strength and elasticity modulus improve.The opposing party Face, the import volume of metal more than divalence can be set to such as 3.0mmol/g (every sheet material) below, more preferably 2.5mmol/g (every sheet material) below, particularly preferably 2.0mmol/g (every sheet material) is below.Thus the transparency can more effectively be improved.

Further, since metal more than divalence is used in manufacturing step by the sheet material of first method provided by the invention The salt from strong acid of salt, so being selected containing being derived from the slave sulphur, chlorine or nitrogen of used strong acid (sulfuric acid, hydrochloric acid or nitric acid) At least one element gone out.The amount of this element also depends on the species of ionic substituent and amount and used is derived from The amount of the salt of strong acid, is, for example, 0.01mmol/g (every sheet material)~0.10mmol/g (every sheet material).Herein, in sheet material The amount of sulphur, chlorine and nitrogen can be measured for example, by fluorescent x-ary analysis.In present embodiment, such as more than above-mentioned divalence In the assay method of metal import volume, by will analysis object be set to sulphur, chlorine or nitrogen, so as to measure the sulphur in sheet material, chlorine and The amount of nitrogen.

＜ is derived from the anion ＞ of strong acid

As noted above it is believed that the salt from strong acid by using metal more than divalence in step (2), in sheet material Anion (such as HSO of the residual from salt₄ ^-), the Yanyuan is from strong acid.The research of people etc. according to the present invention, remains source in sheet material From the anion of strong acid, even if cleaning repeatedly to remove, thus chemical bond is estimated as.In the present invention, in implementation steps (3) When, the remaining anion from strong acid in sheet material is removed by step (3).So the moon of strong acid is derived from obtained sheet material Ion is few or is not detected.

The anion from strong acid is such as HSO in sheet material₄ ^-, HSO₄ ^-It can be analyzed in the form of element sulphur.This Locate, the amount of the sulphur in sheet material for example fluorescent x-ary analysis can be used to be measured.In present embodiment, such as above-mentioned two In the assay method of metal import volume more than valency, by the way that analysis object is set to sulphur, the amount of the sulphur in sheet material can be measured.

The one or more selected in microfibre has from the group from phosphoric acid and from the group of carboxylic acid In the case of ionic substituent, the sulfur content of sheet material is less than 0.02mmol/g (every sheet material).Preferably 0.01mmol/ G (every sheet material) below, cannot more preferably be detected.The reason for this is that if this amount, then can find to suppress cellulose Oxygenolysis, the effect for suppressing xanthochromia.In addition, the content on sheet material, when being known as below certain value, also includes what cannot be detected Situation.

＜ is derived from the ＞ such as the alkali metal of highly basic

In the present invention, in the case of implementation steps (3), it is believed that by being formed in step (3) using weak acid with highly basic Salt, after step (2) processing, with the hydrophilic group of substituent existing for H-type (such as-O^-H⁺) become salt form (such as-O^-Na⁺)。

Refer to for salt form, the element from highly basic can form existing for such as alkali metal or alkali earth metal into Row analysis.Herein, the amount of the alkali metal in sheet material or alkaline-earth metal can be surveyed using such as fluorescent x-ary analysis It is fixed.In present embodiment, such as in the importing quantity measuring method of metal more than above-mentioned divalence, by the way that analysis object is set to Alkali or alkaline earth metal, can measure the amount of the alkali or alkaline earth metal in sheet material.

The alkali metal amount of sheet material is because of the metal more than import volume of substituent, the divalence used and difference, such as For more than 0.05mmol/g (every sheet material).More than preferably 0.10mmol/g (every sheet material), more preferably 0.20mmol/g More than (every sheet material).The reason for this is that more than if the value, then it can find to suppress that carbide occurs during heating, suppress discoloration Effect.On the other hand, alkali metal amount can be set to such as 5.0mmol/g (every sheet material) below, and more preferably 2.5mmol/g is (every Open sheet material) below, particularly preferably 1.0mmol/g (every sheet material) is below.When measuring the element beyond alkali metal amount, this area Technical staff can according to the relevant content of above-mentioned alkali metal, consider chemical equivalent, and determine the content in sheet material.In alkaline earth gold It is more than 0.02mmol/g (every sheet material) in the case of belonging to (divalence).More than preferably 0.05mmol/g (every sheet material), more More than preferably 0.10mmol/g (every sheet material).On the other hand, alkaline-earth metal amount is that can be set to such as 1.0mmol/g (every Sheet material) below, below, particularly preferably 0.25mmol/g (every sheet material) is below by more preferably 0.5mmol/g (every sheet material).

＜ tensile strengths, tensile modulus of elasticity ＞

" tensile strength " and " tensile modulus of elasticity " of sheet material refers to according to JIS P 8135, using cupping machine wet The value measured under the conditions of profit.So-called " wet condition " refer to impregnate object sheet material in ion exchange water 24 it is small when after be used as examination Test piece.By the obtained sheet material of the present invention there is high transparency, and with not handled using metal ion more than divalence Sheet material is compared, and tensile strength in a wetted condition, tensile modulus of elasticity are more excellent.Specifically, by provided by the invention The tensile strength of sheet material in a wetted condition is more than 10.0MPa, is preferably more than 15.0MPa.The reason for this is that if the value More than, then it can be used as packaging material.Upper limit value is not particularly limited, for example, below 200.0MPa, or 100.0MPa Below.It is preferably 1.0GPa in addition, being more than 0.7GPa by the elasticity modulus of sheet material provided by the invention in a wetted condition More than.The reason for this is that more than if the value, then can be used as packaging material.Upper limit value is not particularly limited, and is, for example, Below 10.0GPa, or below 5.0GPa.

＜ water absorption rates ＞

" water absorption rate " of sheet material refer to impregnate the sheet material of 50mm square in ion exchange water 24 it is small when, after dipping The ratio (%) obtained relative to the adiabatic drying mass ratio of sheet material of sheet quality.In addition, " adiabatic drying quality " is Refer to by object at 105 DEG C it is dry 24 it is small when after quality.There is high transparency by the obtained sheet material of the present invention, and with not profit The sheet material handled with metal ion more than divalence is compared, and water absorption rate is lower.Specifically, provided by the invention is passed through The water absorption rate of material is less than 500%, is preferably less than 350%, more preferably less than 200%.The reason for this is that if the value with Under, then it can be used as packaging material.Lower limit is not particularly limited, and is, for example, more than more than 10%, or 50%.

＜ density ＞

" density " of sheet material refer to the sheet material of 50mm square adjusted under the conditions of 23 DEG C, 50%RH humidity 24 it is small when after, Value (the g/cm obtained according to the thickness of sheet material and quality³).The density of the sheet material obtained by the present invention can be according to purposes etc. Appropriate setting, considers intensity and/or the transparency etc., can be set to 0.1~7g/cm³, it is preferably 0.5~5g/cm³, more preferably 1.0 ~3g/cm³。

[the laminating of sheet material, purposes, other]

It can be used by sheet material provided by the invention in the form of the sheet material being only made of a layer of sheet material, can also be Organic layer and/or inorganic layer are formed at least one side and are used in the form of laminated body.By laminating, can further assign To the patience (water resistance, moisture-proof, water repellency) of water.In the case of lamination inorganic layer and organic layer, special limit is sequentially had no Fixed, but the lamination organic layer first on the surface of substrate sheet, the face to form inorganic layer is smooth, makes to be formed can be used in The presence or absence of machine layer the defects of it is less from the viewpoint of, be preferable.Alternatively, it is also possible to containing in addition to organic layer and inorganic layer Other composition layers, such as can also contain and be useful for the bonding for making upper strata and become easy adhesive layer.When laminating, when for When especially paying attention to the purposes of the transparency, the heating stepses for promoting sheet material xanthochromia, UV irradiating steps are not preferably included.By laminating Obtained laminated body preferably includes：Be formed at the substrate sheet layer that is made of sheet material containing microfibre it is at least side, at least 1 Layer inorganic layer and at least 1 layer of organic layer.The number of plies of inorganic layer, organic layer etc. is not particularly limited.It is flexible, the transparency from holding Meanwhile from the viewpoint of obtaining sufficient moisture-proof, inorganic layer is preferably for example set to interact lamination 2 layers~15 with organic layer one side Layer, more preferably 3 layers~7 layers of lamination.

It is not particularly limited, can be enumerated for example as the material into inorganic layer：Aluminium, silicon, magnesium, zinc, tin, nickel, titanium；They Oxide, carbide, nitride, oxycarbide, nitrogen oxides or nitrogen oxycarbide；Or their mixture.Kept from stablizing From the viewpoint of highly moistureproof, more preferably silica, silicon nitride, silicon oxide carbide, silicon oxynitride, nitrogen silicon oxide carbide, aluminium oxide, Aluminium nitride, oxidation of coal aluminium, aluminum oxynitride or their mixture.

It is not particularly limited, can be enumerated for example as the resin used to form organic layer：Epoxy resin, acrylic acid Resin, oxetane resin, silsesquioxane resins, phenol resin, carbamide resin, melmac, unsaturated polyester resin, Silicones, polyurethane resin, silsesquioxane resins or diallyl phthalate ester resin etc..Low water suction in order to obtain The hydrophilic functional groups such as the laminated body of property, hydroxyl, carboxyl or the amino of preferred resin are few.

By sheet material provided by the invention and laminated body, since the transparency is excellent and also has under the conditions of how wet Intensity, therefore the characteristics such as lightweight can be applied flexibly, it is suitable as example：Food, cosmetics, pharmaceuticals, personal computer, household electrical appliances etc. Packaging material.

In addition, by sheet material provided by the invention and laminated body, since optical characteristics is excellent, display member is suitable as Part, illumination component, solar cell or window material or the panel or substrate for them.

More specifically, sheet material and laminated body (hereinafter referred to as " laminated body etc. ") be suitable as flexible display, touch pad, Display, the LED of liquid crystal display, plasma scope, organic el display, field-emitter display, back projection TV etc. Element.In addition, laminated body etc. is suitable as the base used for solar batteries such as silicon systems solar cell, dye-sensitized solar cell Plate., can also be with the lamination such as Obstruct membrane, ITO, TFT as in the purposes of substrate.In addition, be suitable as automobile, rolling stock, The window material of aircraft, house, office block, factory etc..As window material, as needed can also lamination for example：It is fluorine envelope, hard The films such as film or impact resistance, sunproof material.

Laminated body etc. applies flexibly the characteristics such as low linear expansion rate, high resiliency, high intensity, lightweight, is also used as transparent material use Structural material beyond way.Be especially suitable for for example：The automobiles such as windowpane (glazing), built-in material, outside plate, bumper bar, The material of rolling stock, aircraft；Housing, family's electrical accessory, packing material, construction material, engineering materials, the water of personal computer Produce material, other industrial materials etc..

In addition, laminated body etc. can be used for various products.As the example of product, can enumerate for example：Use above-mentioned aobvious Show the computer, tablet terminal machine, mobile phone of element or display；Make use of illumination component light bulb, illumination (ligthing paraphernalia/ Lighting device), indicator light, liquid crystal panel backlight, flashlight, head lamp for bicycle, car inside lamp and instrument panel lamp, traffic Eminence illumination, home-use illumination inside and outside signal lamp, building, school's illumination, medical illumination, factory's illumination, plant Growth lamp, the illumination of image lamp effectiveness, convenience store are when 24 is small or the late into the night business illumination in shop, the indoor photograph of freezer Bright lamp；The various products such as window material, the house of structural material, building, automobile, rolling stock, aircraft, household electrical appliances are used.

Hereinafter, illustrated for the present invention using embodiment, but the scope of the present invention is not limited to embodiment.

Embodiment

(example A1)

The making ＞ of cellulose fibres of the ＜ through importing phosphate

As softwood kraft pulp, paper pulp made of paper [solid constituent 93%, the weight per unit area manufactured using prince 208g/m², sheet, dissociated, according to JIS P8121 measure Canadian Standard Freeness (CSF) 700ml].Above-mentioned In 100 mass parts of adiabatic drying quality of softwood kraft pulp, the mixed aqueous solution of ammonium dihydrogen phosphate and urea is impregnated with, is pressed Squeeze as 49 mass parts of ammonium dihydrogen phosphate, 130 mass parts of urea, to obtain the paper pulp of impregnation liquid.Utilize 105 DEG C of drying machine pair The paper pulp of obtained impregnation liquid is dried, and makes moisture evaporation and carries out predrying.Then, using being set as that 140 DEG C send Wind drying machine heats 10 minutes, imports phosphate in the cellulose in paper pulp, obtains phosphorylation paper pulp.Relative to obtained phosphorus 100 mass parts of adiabatic drying quality of paper pulp are acidified, inject the ion exchange water of 10000 mass parts, it is agitated it is uniformly divided After dissipating, filtering means dehydration is carried out, dehydration sheet material is obtained, repeats this step 2 time, obtain phosphoric acid modification cellulose fibre.Obtained phosphorus The phosphate import volume of acid modified fibre cellulose fiber is 0.98mmol/g.

＜ mechanical treatments ＞

Ion exchange water is added in the paper pulp obtained after cleaning dehydration, forms the pulp suspension of 1.0 mass %.With wet Decline granulating device (Sugino Machine company systems：ULTIMAIZER the pulp suspension) is made by 5 with 245MPa pressure It is secondary, obtain microfibre shape cellulose suspension.

＜ sheet materials ＞

Polyethylene glycol (and the pure medicine company system of light is added in microfibre shape cellulose suspension：Ten thousand) molecular weight 400, makes It becomes 20 mass parts relative to 100 mass parts of microfibre shape cellulose.In addition, so that solid component concentration becomes 0.5 matter The mode of amount % carries out concentration adjustment.So that the completion weight per unit area of sheet material becomes 45g/m²Mode measures suspension, exhibition Open on commercially available acrylic plate, be dried in 35 DEG C, the chamber of 15%RH.In addition, with as given weight per unit area Mode, on acrylic plate configure stop plate.Order more than obtains sheet material, and thickness is 30 μm.

The crosslinking ＞ of ＜ microfibre shape celluloses

Above-mentioned microfibre shape cellulose films are impregnated in using 14~octadecahydrate of aluminum sulfate (Northeast chemistry System) aqueous solution 30 minutes that the aluminum sulfate purity for preparing is 1%, carry out crosslinking Treatment with aluminium.By the sheet material in ion exchange water Middle dipping 15 minutes, is cleaned.Repeat after this cleans 2 times, sheet material to be attached on acrylic plate, in 35 DEG C, 15%RH It is dried in chamber.

(example A2)

In addition to aluminum sulfate aqueous solution concentration is set to 5%, is carried out in the same manner as example A1, obtained sheet material.

(example A3)

In addition to aluminum sulfate aqueous solution concentration is set to 10%, is carried out in the same manner as example A1, obtained sheet material.

(example A4)

In addition to aluminum sulfate aqueous solution concentration is set to 15%, is carried out in the same manner as example A1, obtained sheet material.

(example A5)

As softwood kraft pulp, Oji Paper paper pulp [solid constituent 93%, weight per unit area 208g/ are used m², sheet, dissociated, according to JIS P8121 measure Canadian Standard Freeness (CSF) 700ml].In above-mentioned needle In 100 mass parts of adiabatic drying quality for setting kraft pulp, be impregnated with the mixed aqueous solution of ammonium dihydrogen phosphate and urea, squeezed with As 49 mass parts of ammonium dihydrogen phosphate, 130 mass parts of urea, the paper pulp of impregnation liquid is obtained.Using 105 DEG C of drying machine to obtaining The paper pulp of impregnation liquid be dried, make moisture evaporation and carry out predrying.Then, done using the air-supply for being set as 140 DEG C Dry machine heats 10 minutes, imports phosphate in the cellulose in paper pulp, obtains phosphorylation paper pulp.Relative to obtained phosphorylation 100 mass parts of adiabatic drying quality of paper pulp, inject the ion exchange water of 10000 mass parts, after stirring makes its dispersed, into Row filtering means dehydration, obtains dehydration sheet material, repeats this step 2 time, obtain the high phosphoric acid modification cellulose fibre of phosphate import volume. The phosphate import volume of obtained phosphoric acid modification cellulose fibre is 1.34mmol/g.In addition to being used as raw material, with example A2 is similarly carried out, and has obtained sheet material.

(example A6)

Except using the aqueous solution that the magnesium sulfate purity prepared using magnesium sulfate 7 hydrate (Northeast chemistry system) is 5%, Beyond the crosslinking for carrying out microfibre shape cellulose, carried out in the same manner as example A1, obtained sheet material.

(example A7)

By the undried coniferous tree suitable with 100 mass parts of dry mass shine kraft pulp, TEMPO1.6 mass parts and 10 mass parts of sodium bromide are scattered in 10000 mass parts of water.Then, add 13 mass % Dakin solutions, so that The amount of secondary sodium chlorite becomes 3.5mmol relative to 1.0g paper pulp, starts to react.It is water-soluble that 1.0M sodium hydroxides are added dropwise in the reaction Liquid, makes pH remain 10~11, is considered as reaction at the time of pH is no longer changed and terminates, carboxyl is imported in paper pulp.To the paper pulp Slurry is dehydrated, obtain dehydration sheet material after, inject 5000 mass parts ion exchange water, it is agitated make its dispersed after, Filtering means dehydration is carried out, dehydration sheet material is obtained, repeats this step 2 time, obtain carboxy-modified cellulose fibre.What is obtained is carboxy-modified The carboxyl import volume of cellulose fibre is 1.01mmol/g.In addition to being used as raw material, carry out, obtain in the same manner as example A2 Sheet material.

(example A8)

It is same with example A7 beyond the quantitative change more 8.0mmol of the secondary sodium chlorite of addition except in carboxyl steps for importing Carry out sample, obtained sheet material.The carboxyl import volume of the carboxy-modified cellulose fibre obtained at this time is 1.48mmol/g.

(example A9)

In addition to not carrying out the crosslinking Treatment of microfibre shape cellulose, carried out in the same manner as example A1, obtained sheet material.

(example A10)

In addition to using the phosphoric acid modification cellulose fibre that phosphate import volume is 1.34mmol/g, in the same manner as example A1 Carry out, obtained sheet material.

(example A11)

In addition to not carrying out the crosslinking Treatment of microfibre shape cellulose, carried out in the same manner as example A7, obtained sheet material.

(example A12)

In addition to using the carboxy-modified cellulose fibre that carboxyl import volume is 1.48mmol/g, in the same manner as example A11 Carry out, obtained sheet material.

(evaluation)

＜ methods ＞

To the sheet material made by example A1~12, according to following evaluation method implementation evaluation.

(1) substituent of cellulose surface measures fixed (titration)

Divide the slurry containing fine cellulose fiber for taking the solid constituent containing 0.04g or so in terms of adiabatic drying quality, 50g or so is diluted to using ion exchange water.To the solution while being stirred using magnetic stirring apparatus, while measure addition The value, is become 0.01N sodium hydrate aqueous solutions during minimum by the change of conductivity value during 0.01N sodium hydrate aqueous solutions Dripping quantity be set to the dripping quantity of titration end-point.

At this time, the substitution base unit weight X of cellulose surface is represented by X (mmol/g)=0.01 (mol/l) × V (ml)/W (g).Its In, V is：The dripping quantity (ml) of 0.01N sodium hydrate aqueous solutions, W are：Solid contained by slurry containing fine cellulose fiber into Divide (g).

(2) total light transmittance of sheet material

It is total saturating using haze meter (color technical research institute company system " HM-150 " in village) measure according to JIS standard Ks 7361 Light rate.

(3) mist degree of sheet material

According to JIS standard Ks 7136, mist is measured using haze meter (color technical research institute company system " HM-150 " in village) Degree.

(4) the aluminium import volume in sheet material, magnesium import volume and sulphur import volume

Aluminium, magnesium and the sulphur atom concentration in sheet material are measured using x-ray fluorescence analysis.That is, to sheet material X-ray irradiation When, measure when outer-shell electron transits to what is released when in the hole that the inner electron of aluminium, magnesium or sulphur atom being excited and producing The characteristic X-ray intensity of aluminium, magnesium or sulphur atom, so as to obtain the concentration of aluminium, magnesium or sulphur atom.

Determination condition is as described below.

Analytical equipment：Spectris company systems fluorescent x-ray analyzer (XRF) PW-2404

Determination sample：The circular sample of diameter 27mm

X-ray tube：Rh is managed

To cathode：Rhodium

Analyzing crystal：PE (aluminium), PX1 (magnesium), Ge (sulphur)

Exciting light energy：32kV-125mA

Measure line：Aluminium Al-K α 1, magnesium Mg-K α 1, sulphur S-K α 1

2 θ horns：145.003 (aluminium), 23.100 (magnesium), 110.734 (sulphur)

Minute：58 seconds (aluminium), 50 seconds (magnesium), 54.6 seconds (sulphur)

The filter paper of aluminium import volume known to making, after similarly implementing x-ray fluorescence analysis, the characteristic X that Al atoms are made is penetrated The calibration curve (Fig. 1) of line strength and aluminium import volume.After the filter paper that known magnesium import volume is similarly made for magnesium, then it is made The characteristic X-ray intensity of Mg atoms and the calibration curve (Fig. 2) of magnesium import volume.Known sulphur import volume is similarly made for sulphur Filter paper, and the characteristic X-ray intensity of S atom and the calibration curve (Fig. 3) of sulphur import volume is made.

Then, by the way that the characteristic X-ray intensity of aluminium, magnesium or sulphur atom is substituted into calibration curve, so as to obtain in sheet material The concentration (mmol) of aluminium, magnesium or sulphur atom.Made during with the concentration divided by x-ray fluorescence analysis of obtained aluminium, magnesium or sulphur atom The quality of sheet material, so as to obtain the element import volume (mmol/g) to sheet material.

Wherein, the quality Z of sheet material used in x-ray fluorescence analysis is by Z (g)=W (cm²)×X(g/cm³) × Y (cm) table Show.Wherein, W is：Area (the cm of used sheet material during x-ray fluorescence analysis²), X be：Sheet density (g/cm³), Y be：Piece Material thickness (cm).

In addition, the "-" in table represents micro.

(5) the stretching physical property of sheet material in a wetted condition

According to JIS P 8135, using cupping machine Tensilon (A＆D company systems), drawing in a wetted condition is measured Stretch intensity and tensile modulus of elasticity.Sheet material is impregnated in ion exchange water 24 it is small when after after as test film.

In addition, " swelling/fracture " in table refers to be impregnated in the sheet material swelling after ion exchange water by above-mentioned condition, and Shape can not be kept, the state of stretching physical property can not be measured.

(6) water absorption rate of sheet material

The sheet material of 50mm square is impregnated in ion exchange water 24 it is small when, according to the sheet quality after dipping relative to piece The adiabatic drying mass ratio of material obtains water absorption rate.When by sheet material, drying 24 is small at 105 DEG C, obtained according to dried quality Adiabatic drying quality.

In addition, " swelling/fracture " in table refers to be impregnated in the sheet material swelling after ion exchange water by above-mentioned condition, and Shape can not be kept, the sheet quality state after water suction can not be measured.

(7) density of sheet material

By the sheet material of 50mm square adjusted under the conditions of 23 DEG C, 50%RH humidity 24 it is small when after, according to the thickness of sheet material and Quality obtains the density (g/cm of sheet material³)。

＜ results ＞

As a result it is as shown in the table.Example A9~example A12 is comparative example.

[table 1]

(example B1)

The making ＞ of cellulose fibres of the ＜ through importing phosphate

As softwood kraft pulp, Oji Paper paper pulp [solid constituent 93%, weight per unit area 208g/ are used m², sheet, dissociated, according to JIS P8121 measure Canadian Standard Freeness (CSF) 700ml].In above-mentioned needle In 100 mass parts of adiabatic drying quality for setting kraft pulp, be impregnated with the mixed aqueous solution of ammonium dihydrogen phosphate and urea, squeezed with As 49 mass parts of ammonium dihydrogen phosphate, 130 mass parts of urea, the paper pulp of impregnation liquid is obtained.Using 105 DEG C of drying machine to obtaining The paper pulp of impregnation liquid be dried, make moisture evaporation and carry out predrying.Then, done using the air-supply for being set as 140 DEG C Dry machine heats 10 minutes, imports phosphate in the cellulose in paper pulp, obtains phosphorylation paper pulp.Relative to obtained phosphorylation 100 mass parts of adiabatic drying quality of paper pulp, inject 10000 mass parts ion exchange water, it is agitated make its dispersed after, Filtering means dehydration is carried out, dehydration sheet material is obtained, repeats this step 2 time, obtain phosphoric acid modification cellulose fibre.Obtained phosphoric acid modification The phosphate import volume of cellulose fibre is 0.98mmol/g.

＜ mechanical treatments ＞

Ion exchange water is added in the paper pulp obtained after cleaning dehydration, forms the pulp suspension of 1.0 mass %.With wet Decline granulating device (Sugino Machine company systems：ULTIMAIZER) pulp suspension is passed through with the pressure of 245Mpa 5 times, obtain microfibre shape cellulose suspension.

＜ sheet materials ＞

The crosslinking of ＜ microfibre shape celluloses and the processing ＞ carried out using sodium acetate

By above-mentioned microfibre shape cellulose films, 14~octadecahydrate of aluminum sulfate (Northeast chemistry system) system is being used Standby aluminum sulfate purity is to be impregnated 30 minutes in 5% aqueous solution, and carries out crosslinking Treatment with aluminium.By the sheet material in ion exchange Impregnate 15 minutes, cleaned in water.After repeatedly this is cleaned 2 times, 30 are carried out in sodium acetate (Northeast chemistry system) 5% aqueous solution Minute dipping.The sheet material is impregnated 15 minutes in ion exchange water and is cleaned.After repeatedly this is cleaned 2 times, pressure is attached at On gram force plate, it is dried in 35 DEG C, the chamber of 15%RH.

(example B2)

In addition to sodium acetate aqueous solution concentration is set to 10%, is carried out in the same manner as example B1, obtained sheet material.

(example B3)

In addition to sodium acetate aqueous solution concentration is set to 15%, is carried out in the same manner as example B1, obtained sheet material.

(example B4)

In addition to sodium acetate aqueous solution concentration is set to 20%, is carried out in the same manner as example B1, obtained sheet material.

(example B5)

In addition to sodium acetate aqueous solution concentration is set to 30%, is carried out in the same manner as example B1, obtained sheet material.

(example B6)

It is same with example B1 in addition to using 5% calcium acetate aqueous solution to replace the processing carried out using sodium acetate aqueous solution Carry out sample, obtained sheet material.

(example B7)

In addition to calcium acetate concentration of aqueous solution is set to 20%, is carried out in the same manner as example B6, obtained sheet material.

(example B8)

In addition to using 5% sodium bicarbonate aqueous solution to replace the processing carried out using sodium acetate aqueous solution, with example B1 Similarly carry out, obtained sheet material.

(example B9)

As softwood kraft pulp, Oji Paper paper pulp [solid constituent 93%, weight per unit area 208g/ are used m², sheet, dissociated, according to JIS P8121 measure Canadian Standard Freeness (CSF) 700ml].In above-mentioned needle In 100 mass parts of adiabatic drying quality for setting kraft pulp, be impregnated with the mixed aqueous solution of ammonium dihydrogen phosphate and urea, squeezed with As 49 mass parts of ammonium dihydrogen phosphate, 130 mass parts of urea, the paper pulp of impregnation liquid is obtained.Using 105 DEG C of drying machine to obtaining The paper pulp of impregnation liquid be dried, make moisture evaporation and carry out predrying.Then, done using the air-supply for being set as 140 DEG C Dry machine heats 10 minutes, imports phosphate in the cellulose in paper pulp, obtains phosphorylation paper pulp.Relative to obtained phosphorylation 100 mass parts of adiabatic drying quality of paper pulp, inject the ion exchange water of 10000 mass parts, after stirring makes its dispersed, into Row filtering means dehydration, obtains dehydration sheet material, repeats this step 2 time, obtain the high phosphoric acid modification cellulose fibre of phosphate import volume. The phosphate import volume of obtained phosphoric acid modification cellulose fibre is 1.34mmol/g.In addition to being used as raw material, with example B4 is similarly carried out, and has obtained sheet material.

(example B10)

In addition to using 5% sodium citrate aqueous solution to replace the processing carried out using sodium acetate aqueous solution, with example B1 Similarly carry out, obtained sheet material.

(example B11)

In addition to not handled by sodium acetate, carried out in the same manner as example B1, obtained sheet material.

(example B12)

In addition to not handled by sodium acetate, carried out in the same manner as example B9, obtained sheet material.

(example B13)

In addition to without carrying out the later step of crosslinking Treatment using aluminium, carried out in the same manner as example B1, obtained piece Material.

(example B14)

In addition to without carrying out the later step of crosslinking Treatment using aluminium, carried out in the same manner as example B9, obtained piece Material.

(evaluation)

＜ methods ＞

To the sheet material made by example B1~B14, according to following evaluation method implementation evaluation.

(1) substituent of cellulose surface measures fixed (titration)

Divide and take the slurry containing fine cellulose fiber containing 0.04g or so solid constituents in terms of adiabatic drying quality, make 50g or so is diluted to ion exchange water.To the solution while being stirred using magnetic stirring apparatus, while measure addition The value, is become 0.01N sodium hydrate aqueous solutions during minimum by the change of conductivity value during 0.01N sodium hydrate aqueous solutions Dripping quantity be set to the dripping quantity of titration end-point.

(2) total light transmittance of sheet material

(3) mist degree of sheet material

(4) the front and rear yellow chromaticity of heating

According to JIS standard Ks 7373, using Colour Cute i (Suga Test Instruments Co., Ltd.), survey The front and rear yellow chromaticity of stator material heating.

In addition, heating condition is vacuum drying when progress 4 is small at 200 DEG C.

(5) the sodium import volume in sheet material, sulphur import volume, aluminium import volume and calcium import volume

Sodium, sulphur, aluminium and the calcium atom concentration in sheet material are measured using x-ray fluorescence analysis.That is, penetrated to sheet material irradiation X During line, measure and put when outer-shell electron is transitted to when in the hole that the inner electron of sodium, sulphur, aluminium or calcium atom being excited and producing The characteristic X-ray intensity of the sodium, sulphur, aluminium or the calcium atom that go out, so as to obtain the concentration of sodium, sulphur, aluminium or calcium atom.

Determination condition is as described below.

Determination sample：The circular sample of diameter 27mm

X-ray tube：Rh is managed

To cathode：Rhodium

Analyzing crystal：PX1 (sodium), Ge (sulphur), PE (aluminium), LiF200 (calcium)

Exciting light energy：32kV-125mA (sodium, sulphur, aluminium), 40kV-100mA (calcium)

Measure line：Sodium Na-K α 1, sulphur S-K α 1, aluminium Al-K α 1, calcium Ca-K α 1

2 θ horns：28.009 (sodium), 110.734 (sulphur), 145.003 (aluminium), 132.718 (calcium)

Minute：50 seconds (sodium), 54.6 seconds (sulphur), 58 seconds (phosphorus), 50 seconds (calcium)

The filter paper of sodium import volume known to making, after similarly implementing x-ray fluorescence analysis, the characteristic X that Na atoms are made is penetrated The calibration curve (Fig. 4) of line strength and aluminium import volume.Known sulphur, aluminium or calcium import volume are similarly made for sulphur, aluminium and calcium Filter paper after, then the characteristic X-ray intensity of S, Al or Ca atom and calibration curve (Fig. 3, the figure of sulphur, aluminium or calcium import volume is made 1st, Fig. 5).

Then, by the way that the characteristic X-ray intensity of sodium, sulphur, aluminium or calcium is substituted into calibration curve, so as to obtain in sheet material Sodium, sulphur, the concentration (mmol) of aluminium or calcium.Used during with the concentration divided by x-ray fluorescence analysis of obtained sodium, sulphur, aluminium or calcium Sheet material quality, so as to obtain the element import volume (mmol/g) to sheet material.

(6) the stretching physical property (drying condition and wet condition) of sheet material

According to JIS P 8113 and JIS P 8135, cupping machine Tensilon (A＆D company systems), measure stretching are used Intensity, tensile modulus of elasticity and tensile elongation.Usual conditions be by under 23 DEG C, 50%RH adjust humidity 24 it is small when after piece Material is as test film.Wet condition be sheet material is impregnated in ion exchange water 24 it is small when after be set to test film.

(7) water absorption rate of sheet material

(8) density of sheet material

＜ results ＞

As a result it is as shown in the table.Example B13 and example B14 is comparative example.

[table 2]

Claims

1. a kind of sheet material, it contains metal more than microfibre and divalence with ionic substituent, its mist degree is Less than 10.0%.

2. sheet material as claimed in claim 1, wherein, the content of metal more than divalence is more than 0.10mmol/g.

3. sheet material as claimed in claim 1 or 2, wherein, microfibre is that have from the group from phosphoric acid, from carboxylic acid Microfibre shape cellulose of the one or more selected in group and group from sulfuric acid as ionic substituent.

4. such as sheet material according to any one of claims 1 to 3, its tensile strength in a wetted condition is more than 10.0MPa.

5. such as sheet material according to any one of claims 1 to 4, its tensile modulus of elasticity in a wetted condition for 0.7GPa with On.

6. a kind of sheet material, it contains metal more than microfibre and divalence with ionic substituent, wherein, xanthochromia degree becomes Change (Δ YI) and meet following formula (1)：

Δ YI=YI₂-YI₁≤20…(1)

Wherein, YI₁Represent the yellow chromaticity before vacuum drying, YI when progress 4 is small at 200 DEG C₂When representing that progress 4 is small at 200 DEG C Yellow chromaticity after vacuum drying.

7. sheet material as claimed in claim 6, wherein, the content of metal more than divalence is more than 0.10mmol/g.

8. sheet material as claimed in claims 6 or 7, wherein, microfibre is that have from the group from phosphoric acid, from carboxylic acid Microfibre shape cellulose of the one or more selected in group and group from sulfuric acid as ionic substituent.

9. the sheet material as any one of claim 6~8, it contains at least one selected from alkali or alkaline earth metal Kind.

10. the sheet material as any one of claim 6~9, wherein, microfibre be have from the group from phosphoric acid and Microfibre shape cellulose of the one or two selected in group from carboxylic acid as ionic substituent, and sulfur content is Below 0.05mmol/g.

11. the sheet material as any one of claim 6~10, its tensile strength in a wetted condition for 20.0MPa with On.

12. the sheet material as any one of claim 6~11, its tensile modulus of elasticity in a wetted condition is 0.7GPa More than.

13. a kind of laminated body, it at least forms inorganic layer the sheet material any one of claim 1~12 on side And/or organic layer.

14. a kind of manufacture method of sheet material, it includes：The step of sheet material being prepared from the microfibre with ionic substituent； And the step of being handled using the salt from strong acid of metal more than divalence prepared sheet material.

15. the manufacture method of sheet material as claimed in claim 14, it includes：The salt pair further formed using weak acid with highly basic The step of processed sheet material is handled.